JP6766016B2 - Method for producing tin-containing oxide glass - Google Patents
Method for producing tin-containing oxide glass Download PDFInfo
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- JP6766016B2 JP6766016B2 JP2017153774A JP2017153774A JP6766016B2 JP 6766016 B2 JP6766016 B2 JP 6766016B2 JP 2017153774 A JP2017153774 A JP 2017153774A JP 2017153774 A JP2017153774 A JP 2017153774A JP 6766016 B2 JP6766016 B2 JP 6766016B2
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- 239000000075 oxide glass Substances 0.000 title claims description 36
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000002243 precursor Substances 0.000 claims description 83
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 80
- 238000002844 melting Methods 0.000 claims description 47
- 230000008018 melting Effects 0.000 claims description 47
- 229910052718 tin Inorganic materials 0.000 claims description 32
- 239000007858 starting material Substances 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- -1 B 2 O 3 Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 80
- 239000011521 glass Substances 0.000 description 76
- 239000002419 bulk glass Substances 0.000 description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 58
- 235000011007 phosphoric acid Nutrition 0.000 description 46
- 239000000203 mixture Substances 0.000 description 43
- 239000012856 weighed raw material Substances 0.000 description 37
- 239000000155 melt Substances 0.000 description 36
- 238000002834 transmittance Methods 0.000 description 35
- 229910001220 stainless steel Inorganic materials 0.000 description 34
- 239000010935 stainless steel Substances 0.000 description 34
- 239000013585 weight reducing agent Substances 0.000 description 34
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 16
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 15
- 229910001887 tin oxide Inorganic materials 0.000 description 15
- 239000011734 sodium Substances 0.000 description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 11
- 229910018068 Li 2 O Inorganic materials 0.000 description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 9
- 229910001386 lithium phosphate Inorganic materials 0.000 description 8
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000003016 phosphoric acids Chemical class 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910004837 P—Sn Inorganic materials 0.000 description 4
- MQZGYYYBCTXEME-UHFFFAOYSA-N [Rb][Rb] Chemical compound [Rb][Rb] MQZGYYYBCTXEME-UHFFFAOYSA-N 0.000 description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004031 devitrification Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 238000007496 glass forming Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- VDVJQFLGCFFFBP-UHFFFAOYSA-N 2,3-dihydropyrrole-1-carboxylic acid Chemical compound OC(=O)N1CCC=C1 VDVJQFLGCFFFBP-UHFFFAOYSA-N 0.000 description 1
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000299 transition metal carbonate Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
Description
本発明は、スズ含有酸化物ガラスの低温溶融製造方法に関する。 The present invention relates to a method for producing a tin-containing oxide glass by melting at a low temperature.
近年、３次元レーザプリンタに代表されるように、簡便に複雑な形状を作り上げられる技術に注目が集まっている。このような材料としては、一般的には、有機高分子が用いられているが、ガス透過性や化学的耐久性の観点からは、無機材料、特に成型加工が容易な酸化物ガラスが望ましい。しかしながら、通常の酸化物ガラスは、酸化物原料粉末を一旦１０００℃以上の高温で溶融し、アモルファス化する一般的な溶融法で作製されており、このような用途には不適である。 In recent years, as represented by a three-dimensional laser printer, attention has been focused on a technique for easily creating a complicated shape. As such a material, an organic polymer is generally used, but from the viewpoint of gas permeability and chemical durability, an inorganic material, particularly an oxide glass that can be easily molded, is desirable. However, ordinary oxide glass is produced by a general melting method in which an oxide raw material powder is once melted at a high temperature of 1000 ° C. or higher and amorphized, and is not suitable for such applications.
また、１０００℃以上の高温で溶融する場合には、溶融に用いる容器から成分のコンタミが懸念され、設計通りの組成を得ることが難しく、ゆえに高品質化が難しいという問題がある。 Further, when melting at a high temperature of 1000 ° C. or higher, there is a concern about contamination of components from the container used for melting, and it is difficult to obtain the composition as designed, and therefore it is difficult to improve the quality.
一方で、酸化物ガラスの中にも、５５０℃以下の低温で溶融する低融点ガラスというガラス部材が存在する。この低融点ガラスは、低融点化成分として鉛を多く含有しており、主として電子部品の被覆・封止材料等として用いられてきた。特に、最近のハイパワーLEDの開発に伴い、従来用いられてきた有機封止材料では適応が困難なデバイスが生じてきている。特に、可視領域の透明性と低温での軟化特性を兼ね備えた低融点酸化物ガラスが必要とされている。しかしながら、前述の低融点酸化物ガラスに含まれる鉛成分は、環境負荷物質としてRoHS規制などにより禁止されたり、規制外用途でも使用が敬遠されており、その利用が困難である。そのため、鉛を含まない低温で成型加工が可能な低融点酸化物ガラスの開発は、産業界から切望されている。 On the other hand, even in oxide glass, there is a glass member called low melting point glass that melts at a low temperature of 550 ° C. or lower. This low melting point glass contains a large amount of lead as a low melting point component, and has been mainly used as a coating / sealing material for electronic parts. In particular, with the recent development of high-power LEDs, there are some devices that are difficult to adapt with the conventionally used organic encapsulant materials. In particular, there is a need for low melting point oxide glass that has both transparency in the visible region and softening properties at low temperatures. However, the lead component contained in the above-mentioned low melting point oxide glass is prohibited as an environmentally hazardous substance by RoHS regulations and the like, and its use is avoided even in non-regulated applications, and its use is difficult. Therefore, the development of low melting point oxide glass that does not contain lead and can be molded at a low temperature is eagerly desired by the industrial world.
このようなRoHS規制の課題を解決するため、鉛を含む低融点酸化物ガラスの代替ガラスとして、ビスマス系、バナジウム系、リン系等の低融点酸化物ガラス（例えば、特許文献１〜４）が開発されている。この中でビスマス系低融点酸化物ガラスの主成分Ｂｉは現在規制されていないが、将来規制対象になる可能性の問題がある。バナジウム系低融点酸化物化ガラスは黒色に着色したガラスとなり、透明性を求める用途には使用できない問題がある。リン系低融点酸化物ガラスは規制対象になる可能性は少なく、透明性ガラスを作製できる点で魅力がある。 In order to solve such the problem of RoHS regulation, low melting point oxide glass such as bismuth type, vanadium type and phosphorus type (for example, Patent Documents 1 to 4) is used as an alternative glass for low melting point oxide glass containing lead. It is being developed. Among these, the main component Bi of bismuth-based low melting point oxide glass is not currently regulated, but there is a problem that it may be subject to regulation in the future. The vanadium-based low melting point oxide glass becomes a glass colored black, and has a problem that it cannot be used for applications requiring transparency. Phosphorus-based low melting point oxide glass is unlikely to be subject to regulation, and is attractive in that transparent glass can be produced.
リン系低融点酸化物ガラスの代表組成としては、リン以外に亜鉛を含有したＰ−Ｚｎ系、スズを含有したＰ−Ｓｎ系が代表的であるが、亜鉛を主体に含有したＰ−Ｚｎ系はスズ含有のＰ−Ｓｎ系に比べ耐水性（化学的耐久性）に乏しい欠点があった。そのため、応用には耐水性を要求されない条件下での適用や、そのガラスに別途コーティングやカバーを掛けたりする必要があった。 Typical compositions of phosphorus-based low melting point oxide glass are P-Zn-based, which contains zinc in addition to phosphorus, and P-Sn-based, which contains tin, but P-Zn-based, which mainly contains zinc. Has a drawback of poor water resistance (chemical durability) as compared with the tin-containing P-Sn system. Therefore, it is necessary to apply the glass under conditions that do not require water resistance, or to separately coat or cover the glass.
Ｐ−Ｚｎ系に比べ耐水性に優れるスズ含有のＰ−Ｓｎ系も条件によっては失透しやすく、そのためにガラスが白濁する問題があり、Ｐ−Ｓｎ系リン酸ガラスの結晶化を抑制し、耐水性を上げることが必要とされる。 The tin-containing P-Sn system, which has better water resistance than the P-Zn system, also easily devitrifies depending on the conditions, which causes a problem that the glass becomes cloudy, and suppresses the crystallization of the P-Sn phosphoric acid glass. It is necessary to increase the water resistance.
本発明は、鉛を含まず透明性かつ耐水性を有する酸化物ガラスを５５０℃以下の低温溶融にて製造する方法を提供することを目的とする。 An object of the present invention is to provide a method for producing lead-free, transparent and water-resistant oxide glass by melting at a low temperature of 550 ° C. or lower.
本発明者らは、上記のような事情を鑑み、鋭意検討を重ねた結果、Ｐ２Ｏ５、ＳｎＯ、アルカリ金属酸化物Ｒ２Ｏ（Ｒ=Ｌｉ、Ｎａ、Ｋ、Ｃｓ、Ｒｂ・・・）及び希土類酸化物ＭｘＯｙ（Ｍ=Ｃｅ、Ｌａ、Ｙ、Ｎｄ、・・・）（ｘ、ｙ＝１，２，３，・・・）の出発原料を特定の割合で混合し、得られた前駆体を熱処理することにより、５５０℃以下の溶融温度で、透明性かつ耐水性を有するスズ含有酸化物ガラス部材が得られることを見出し、さらに検討を加えて本発明を完成するに至った。 In view of the above circumstances, the present inventors have conducted diligent studies, and as a result, P 2 O 5 , SnO, alkali metal oxide R 2 O (R = Li, Na, K, Cs, Rb ... ) And the starting materials of the rare earth oxide M x Oy (M = Ce, La, Y, Nd, ...) (X, y = 1, 2, 3, ...) Are mixed in a specific ratio. By heat-treating the obtained precursor, it was found that a transparent and water-resistant tin-containing oxide glass member can be obtained at a melting temperature of 550 ° C. or lower, and further studies are carried out to complete the present invention. I arrived.
本発明のスズ含有酸化物ガラスの製造方法は、酸化物基準のモル％表示で、Ｐ２Ｏ５：３５〜５５モル％、ＳｎＯ：３４〜５９モル％、アルカリ金属酸化物Ｒ２Ｏ（Ｒ=Ｌｉ、Ｎａ、Ｋ、Ｃｓ、Ｒｂ・・・）：０．２〜２０モル％、希土類酸化物ＭｘＯｙ（Ｍ=Ｃｅ、Ｌａ、Ｙ、Ｎｄ、・・・）（ｘ、ｙ＝１，２，３，・・・）：０〜５モル％、ＳｉＯ ２ 、Ａｌ ２ Ｏ ３ 、Ｂ ２ Ｏ ３ 、ＺｎＯ、アルカリ土類金属酸化物ＲＯ（Ｒ＝Ｍｇ、Ｃａ、Ｓｒ、Ｂａ・・・）及び遷移金属酸化物の合計：５モル％以下となるように、リン酸類及びスズ化合物及びアルカリ金属化合物を含む原料を混合してすべての出発原料が均一に分散した液である前駆体を作製し、得られた前駆体を５５０℃以下のアモルファスになる溶融温度で熱処理する、ことを特徴とするものである。 Method for producing a tin-containing oxide glass of the present invention, as represented by mol% based on oxides, P 2 O 5: 35~55 mol%, SnO: thirty-four to fifty-nine mol%, the alkali metal oxides R 2 O (R = Li, Na, K, Cs, Rb ...): 0.2 to 20 mol% , rare earth oxide M x Oy (M = Ce, La, Y, Nd, ...) (X, y = 1,2,3, ...): 0 to 5 mol% , SiO 2 , Al 2 O 3 , B 2 O 3 , ZnO, alkaline earth metal oxide RO (R = Mg, Ca, Sr, Ba.・ ・) And transition metal oxides: A precursor that is a liquid in which raw materials containing phosphoric acids, tin compounds, and alkali metal compounds are mixed so that all starting materials are uniformly dispersed so as to be 5 mol% or less. Is produced, and the obtained precursor is heat-treated at a melting temperature at which it becomes amorphous at 550 ° C. or lower.
なお、前記溶融温度が３５０〜５５０℃であり、溶融時間が１０〜１２０分であることが好ましい。 It is preferable that the melting temperature is 350 to 550 ° C. and the melting time is 10 to 120 minutes.
本発明のスズ含有酸化物ガラスの製造方法によれば、従来のガラスフリットのような１０００℃以上の高温溶融法を用いて作製することなく、透明性と耐水性を兼ね備えた酸化物ガラスを５５０℃以下の低温溶融で製造することができる。また、本発明の方法によれば、多様な形状のスズ含有酸化物ガラスを低温で作製することが可能である。この方法は、雰囲気制御をおこなった高温溶融法を用いないため、作製に係るエネルギーを削減できるという点で有利である。また、５５０℃以下の低温で溶融するため、溶融に用いる容器を侵食する恐れが少ないので、容器からの成分溶出が殆どない、したがって従来の１０００℃付近の高温溶融に比べ容器からのコンタミが少なく、高品質なガラスが作製できる利点がある。 According to the method for producing tin-containing oxide glass of the present invention, 550 oxide glass having both transparency and water resistance is produced without producing by using a high-temperature melting method of 1000 ° C. or higher as in the conventional glass frit. It can be manufactured by melting at a low temperature of ° C or lower. Further, according to the method of the present invention, tin-containing oxide glass having various shapes can be produced at a low temperature. Since this method does not use the high-temperature melting method in which the atmosphere is controlled, it is advantageous in that the energy required for production can be reduced. Further, since it melts at a low temperature of 550 ° C. or lower, there is little risk of eroding the container used for melting, so that there is almost no elution of components from the container. There is an advantage that high quality glass can be produced.
本発明の方法で得られるスズ含有酸化物ガラス部材は、透明性、及び耐水性を兼ね備えており、さらに溶融温度が５５０℃以下と低いため、種々の形状を有するガラス部材としての適用が期待される。また、本発明のスズ含有酸化物ガラス部材は、照明、光学部材、蛍光標識、ガラスコーティング、封止材、陶磁器、装飾用ガラス等にも使用可能である。 The tin-containing oxide glass member obtained by the method of the present invention has both transparency and water resistance, and has a low melting temperature of 550 ° C. or lower, so that it is expected to be applied as a glass member having various shapes. To. Further, the tin-containing oxide glass member of the present invention can also be used for lighting, optical members, fluorescent labels, glass coatings, sealing materials, ceramics, decorative glass and the like.
以下に本発明の実施形態を説明する。この実施形態では、例えばLED素子封着用粉末ガラスとして用いられる場合のスズ含有酸化物ガラスの低温溶融製造方法及びスズ含有酸化物ガラス部材について述べる。 An embodiment of the present invention will be described below. In this embodiment, for example, a method for producing a tin-containing oxide glass at a low temperature and a tin-containing oxide glass member when used as a powder glass for sealing an LED element will be described.
本発明におけるスズ含有酸化物ガラス部材は、必須成分としてＰ２Ｏ５、ＳｎＯ、アルカリ金属酸化物Ｒ２Ｏ（例えばＫ２Ｏ、Ｎａ２Ｏ、Ｌｉ２Ｏ、Ｃｓ２Ｏ、Ｒｂ２Ｏ等)の1種類以上、および希土類酸化物ＭｘＯｙ（例えばＣｅＯ２、Ｙ２Ｏ３、Ｌａ２Ｏ３、Ｎｄ２Ｏ３等）（ｘ、ｙ＝１，２，３・・・）の1種類以上が含有されている。 The tin-containing oxide glass member in the present invention contains P 2 O 5 , SnO, alkali metal oxide R 2 O (for example, K 2 O, Na 2 O, Li 2 O, Cs 2 O, Rb 2 O, etc.) as essential components. ), And rare earth oxides M x O y (eg, CeO 2 , Y 2 O 3 , La 2 O 3 , Nd 2 O 3, etc.) (x, y = 1, 2, 3 ...) Contains one or more types.
また、本発明のスズ含有酸化物ガラス部材は、任意成分としてＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３、ＺｎＯおよびアルカリ土類金属酸化物ＲＯ（例えばＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ等）、が含有されても良い。 Further, the tin-containing oxide glass member of the present invention contains SiO 2 , Al 2 O 3 , B 2 O 3 , ZnO and an alkaline earth metal oxide RO (for example, MgO, CaO, SrO, BaO, etc.) as optional components. May be contained.
さらに、本発明のスズ含有酸化物ガラス部材は、透明性を阻害しない範囲でＦｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｖ、Ｃｒ等の遷移金属酸化物が含有されても良い。 Further, the tin-containing oxide glass member of the present invention may contain transition metal oxides such as Fe, Co, Ni, Cu, V and Cr as long as the transparency is not impaired.
スズ含有酸化物ガラス部材の組成範囲は、酸化物基準のモル％表示で、Ｐ２Ｏ５が３５〜５５モル％、好ましくは３５〜４５モル％、ＳｎＯが３４〜５９モル％、好ましくは４４〜５４モル％、Ｒ２Ｏ(例えばＫ２Ｏ、Ｎａ２Ｏ、Ｌｉ２Ｏ、Ｃｓ２Ｏ、Ｒｂ２Ｏ等)が０．２〜２０モル％、好ましくは５〜１５モル％であり、さらに、ＭｘＯｙ（例えばＣｅＯ２、Ｙ２Ｏ３、Ｌａ２Ｏ３、Ｎｄ２Ｏ３等）（ｘ、ｙ＝１，２，３・・・）が０．１〜５モル％、好ましくは０．１〜２モル％である。 The composition range of the tin-containing oxide glass member is expressed in mol% based on the oxide, P 2 O 5 is 35 to 55 mol%, preferably 35 to 45 mol%, SnO is 34 to 59 mol%, preferably 44. ~ 54 mol%, R 2 O (eg K 2 O, Na 2 O, Li 2 O, Cs 2 O, Rb 2 O, etc.) is 0.2 to 20 mol%, preferably 5 to 15 mol% . Further , M x O y (for example, CeO 2 , Y 2 O 3 , La 2 O 3 , Nd 2 O 3, etc.) (x, y = 1, 2, 3 ...) Is 0.1 to 5 mol%, It is preferably 0.1 to 2 mol%.
全成分の合計が１００モル％になるように、任意成分は酸化物基準のモル％表示で、０．１〜５モル％、好ましくは０．１〜２モル％の範囲で含有されても良い。 The optional component may be contained in the range of 0.1 to 5 mol%, preferably 0.1 to 2 mol% in terms of oxide-based mol% so that the total of all components is 100 mol%. ..
次に各成分の範囲理由を述べる。
Ｐ２Ｏ５はガラス形成成分であり、低温溶融促進成分でもある。３５モル％未満の場合は５５０℃以下の溶融温度では十分溶融せず、ガラス化が困難である。５５モル％より多いと耐水性が著しく低下する。好ましいＰ２Ｏ５の範囲は３５〜４５モル％である。
Next, the reason for the range of each component will be described.
P 2 O 5 is a glass forming component and also a low temperature melting promoting component. If it is less than 35 mol%, it does not melt sufficiently at a melting temperature of 550 ° C. or lower, and vitrification is difficult. If it is more than 55 mol%, the water resistance is significantly lowered. The preferred range for P 2 O 5 is 35-45 mol%.
ＳｎＯはガラス形成成分である。３４モル％未満の場合は耐水性が低下する。５９モル％より多いと５５０℃以下での溶融温度では溶融せず、ガラス化が困難である。好ましいＳｎＯの範囲は４４〜５４モル％である。 SnO is a glass-forming component. If it is less than 34 mol%, the water resistance is lowered. If it is more than 59 mol%, it does not melt at a melting temperature of 550 ° C. or lower, and vitrification is difficult. The preferred SnO range is 44-54 mol%.
Ｒ２Ｏ（Ｒ=Ｌｉ、Ｎａ、Ｋ、Ｃｓ、Ｒｂ・・・）はガラス形成修飾成分であり、低温溶融促進成分でもある。１種類以上のＲ２Ｏの合計が０．２モル％未満の場合はガラスが失透しやすくなる。２０モル％より多い場合はガラスの耐水性が低下し、ガラスの安定性が低下する。好ましいＲ２Ｏの範囲は５〜１５モル％である。 R 2 O (R = Li, Na, K, Cs, Rb ...) Is a glass forming modifying component and a low temperature melting promoting component. 1 Total or more R 2 O tends glass devitrification of less than 0.2 mol%. If it is more than 20 mol%, the water resistance of the glass is lowered and the stability of the glass is lowered. Preferred R 2 O in the range from 5 to 15 mol%.
ＭｘＯｙ（例えばＣｅＯ２、Ｙ２Ｏ３、Ｌａ２Ｏ３、Ｎｄ２Ｏ３等）（ｘ、ｙ＝１，２，３・・・）は、本発明で発見したガラスの耐水性を向上させる特徴的な成分である。０．１モルより少ない場合は耐水性向上の効果が認められない。５モル％よりも多い場合はガラスの溶融温度が上がり、５５０℃の溶融ではガラス化しにくくなる。好ましいＭｘＯｙの範囲は０．１〜２モル％である。 M x O y (for example, CeO 2 , Y 2 O 3 , La 2 O 3 , Nd 2 O 3, etc.) (x, y = 1, 2, 3 ...) Is the water resistance of the glass found in the present invention. It is a characteristic ingredient that improves. If it is less than 0.1 mol, the effect of improving water resistance is not recognized. If it is more than 5 mol%, the melting temperature of the glass rises, and melting at 550 ° C makes it difficult to vitrify. The preferred range of M x O y is from 0.1 to 2 mol%.
任意成分ＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３、ＺｎＯおよびアルカリ土類金属酸化物ＲＯ（例えばＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ等）、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｖ、Ｃｒ等の遷移金属酸化物は、５５０℃での溶融性、及び透明性を妨げない範囲０．１〜５モル％の範囲で添加しても良い。好ましくは０．１〜２モル％の範囲である。 Transition of optional components SiO 2 , Al 2 O 3 , B 2 O 3 , ZnO and alkaline earth metal oxide RO (for example, MgO, CaO, SrO, BaO, etc.), Fe, Co, Ni, Cu, V, Cr, etc. The metal oxide may be added in a range of 0.1 to 5 mol % that does not interfere with the meltability at 550 ° C. and the transparency. It is preferably in the range of 0.1 to 2 mol%.
本発明のスズ含有酸化物ガラス部材の製造方法は、出発原料として、Ｐ２Ｏ５はリン酸類、ＳｎＯはスズ化合物、Ｒ２Ｏはアルカリ金属化合物、及びＭｘＯｙは希土類化合物を用い、所望の組成に混合して前駆体を作製し、その前駆体を５５０℃以下の溶融温度で熱処理し、ガラス化する方法である。 The method of manufacturing a tin-containing oxide glass member of the present invention, as a starting material, P 2 O 5 is phosphoric acids, SnO tin compounds, R 2 O is an alkali metal compound, and M x O y is used a rare earth compound, This is a method in which a precursor is prepared by mixing with a desired composition, and the precursor is heat-treated at a melting temperature of 550 ° C. or lower to vitrify it.
Ｐ２Ｏ５の出発原料としてはリン酸類を用いることができる。
リン酸類はガラスを安定化させる成分であり、透明性を有するガラスを製造できる組成範囲が広いことから、オルトリン酸またはピロリン酸、ポリリン酸を用いることが好ましい。出発原料としてオルトリン酸を用いる場合には、水を含有する状態のものを使用してもよい。オルトリン酸における水の含有量は特に限定されず、例えば、無水オルトリン酸、８５％リン酸等を使用することが可能である。
Phosphoric acids can be used as a starting material for P 2 O 5 .
Phosphoric acids are components that stabilize glass, and since the composition range in which transparent glass can be produced is wide, it is preferable to use orthophosphoric acid, pyrophosphoric acid, or polyphosphoric acid. When orthophosphoric acid is used as a starting material, one containing water may be used. The content of water in orthophosphoric acid is not particularly limited, and for example, anhydrous orthophosphoric acid, 85% phosphoric acid and the like can be used.
ＳｎＯの出発原料としてはスズ化合物を用いることができる。
スズ化合物は、リン酸類と同じくガラスネットワークを形成する成分である。透明性を有するガラスを製造できる組成範囲が広い酸化第一錫、ピロリン酸スズ、シュウ酸スズ、酢酸スズ等が好ましい。
A tin compound can be used as a starting material for SnO.
Similar to phosphoric acids, tin compounds are components that form a glass network. Stannous oxide, tin pyrophosphate, tin oxalate, tin acetate and the like having a wide composition range capable of producing transparent glass are preferable.
アルカリ金属酸化物Ｒ２Ｏの出発原料としてはアルカリ金属化合物を用いることができる。
アルカリ金属化合物は、ガラス修飾酸化物となり、ガラスの溶融温度を下げ、ガラスを安定化させる成分である。リン酸類と相溶性のあるピロリン酸塩、リン酸水素二塩、リン酸二水素塩、炭酸塩、水酸化物が好ましい。
The starting material for the alkali metal oxides R 2 O may be used an alkali metal compound.
The alkali metal compound becomes a glass-modified oxide and is a component that lowers the melting temperature of the glass and stabilizes the glass. Pyrophosphate, hydrogen phosphate dihydrogen, dihydrogen phosphate, carbonate, and hydroxide compatible with phosphoric acids are preferable.
希土類酸化物ＭｘＯｙの出発原料としては希土類元素化合物を用いることができる。
希土類元素化合物は、ガラスを安定化させ、耐水性を向上させる特徴的な成分である。リン酸類と相溶性のある酸化物、水酸化物、硝酸塩が好ましい。
The starting materials of the rare earth oxide M x O y may be used a rare earth element compound.
Rare earth element compounds are characteristic components that stabilize glass and improve water resistance. Oxides, hydroxides and nitrates that are compatible with phosphoric acids are preferable.
任意成分としてＳｉＯ２、Ａｌ２Ｏ３、Ｂ２Ｏ３、ＺｎＯ等を用いる場合は、酸化物、リン酸塩、炭酸塩、水酸化物を用いることができる。 When SiO 2 , Al 2 O 3 , B 2 O 3 , ZnO or the like is used as an optional component, oxides, phosphates, carbonates, hydroxides and the like can be used.
任意成分としてアルカリ土類金属酸化物ＲＯ（例えばＣａＯ、ＭｇＯ、ＳｒＯ、ＢａＯ等）を用いる場合の出発原料は、そのアルカリ土類元素の、酸化物、リン酸塩、炭酸塩、水酸化物の化合物を用いることができる。 When alkaline earth metal oxide RO (for example, CaO, MgO, SrO, BaO, etc.) is used as an optional component, the starting material is an oxide, phosphate, carbonate, hydroxide of the alkaline earth element. Compounds can be used.
任意成分としてＦｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｖ、Ｃｒ等の遷移金属酸化物を用いる場合の出発原料は、その遷移金属の、酸化物、リン酸塩、炭酸塩、水酸化物の化合物を用いることができる。 When a transition metal oxide such as Fe, Co, Ni, Cu, V, or Cr is used as an optional component, a compound of the transition metal oxide, phosphate, carbonate, or hydroxide is used as a starting material. be able to.
バッチ成分の還元を防ぎ、溶解を促進するために酸化剤を添加することができる。酸化剤は例えば硝酸ナトリウム、硝酸カリウム、硝酸バリウム、酸化マンガン等がある。 Oxidizing agents can be added to prevent reduction of batch components and promote dissolution. Examples of the oxidizing agent include sodium nitrate, potassium nitrate, barium nitrate, manganese oxide and the like.
混合に用いる容器は吸湿性の無い容器であれば任意の容器を用いることができるが、溶融工程まで連続で使用できることが望ましく、ホウ珪酸ガラス製容器が好ましい。
単一容器で連続使用することにより、コンタミの少ないガラス作製が可能となる。
Any container can be used as long as it is a non-hygroscopic container, but it is desirable that the container can be used continuously until the melting step, and a borosilicate glass container is preferable.
By continuously using it in a single container, it is possible to produce glass with less contamination.
出発原料の混合順序は、すべての出発原料が均一に分散した前駆体を得ることができれば、いかなる順序で混合してもよい。出発原料が、リン酸類、スズ化合物、アルカリ金属化合物、及び希土類元素化合物の４成分の場合には、例えば、４成分を一度に混合してもよいし、先に２成分を混合し、そこに残りの２成分を順番に添加して混合してもよいし、先に３成分を一度に混合し、そこに残りの１成分を添加して混合してもよい。 The starting material may be mixed in any order as long as a precursor in which all the starting materials are uniformly dispersed can be obtained. When the starting material is four components of a phosphoric acid, a tin compound, an alkali metal compound, and a rare earth element compound, for example, the four components may be mixed at once, or the two components may be mixed first, and then there. The remaining two components may be added in order and mixed, or the three components may be mixed at once and the remaining one component may be added and mixed.
出発原料として、上記４成分に加えて他の成分を含む場合には、他の成分は上記のどの段階で添加してもよい。例えば、上記４成分及び他の成分を一度に混合してもよいし、先に４成分の内の１成分及び他の成分を混合し、そこに残りの３成分を添加して混合してもよいし、先に４成分の内の２成分及び他の成分を混合し、そこに残りの２成分を添加して混合しても良い。 When other components are included as a starting material in addition to the above four components, the other components may be added at any of the above steps. For example, the above four components and other components may be mixed at once, or one of the four components and the other component may be mixed first, and the remaining three components may be added and mixed. Alternatively, two of the four components and the other components may be mixed first, and the remaining two components may be added and mixed.
混合の手法は例えばスターラー回転子、攪拌ミキサー、自転公転攪拌等を用いることができる。また攪拌時に混合液を加熱しながら攪拌しても良い。 As a mixing method, for example, a stirrer rotor, a stirring mixer, rotation / revolution stirring, or the like can be used. Further, the mixed solution may be stirred while being heated at the time of stirring.
次に、出発原料を混合して得られた前駆体を所定の温度条件で溶融し、急冷することでスズ含有酸化物ガラスを作製する。 Next, the precursor obtained by mixing the starting materials is melted under a predetermined temperature condition and rapidly cooled to prepare a tin-containing oxide glass.
溶融温度（加熱温度）及び溶融時間は、用いる出発原料により適宜決定することができる。溶融温度は、通常３５０〜５５０℃である。３５０℃未満の場合は温度不足によりガラス化が不十分であり、５５０℃より高い場合はガラスの失透が起こりやすくなる。好ましい溶融温度は４００〜５００℃である。 The melting temperature (heating temperature) and melting time can be appropriately determined depending on the starting material used. The melting temperature is usually 350 to 550 ° C. If the temperature is lower than 350 ° C, vitrification is insufficient due to insufficient temperature, and if the temperature is higher than 550 ° C, devitrification of the glass is likely to occur. The preferred melting temperature is 400-500 ° C.
また、溶融時間は、５分〜１２０分である。５分未満の場合は完全に溶融せず溶け残りや気泡が残留する。１２０分より長い場合はガラスの失透が起こりやすくなる。好ましい溶融時間は１０分〜６０分程度である。 The melting time is 5 minutes to 120 minutes. If it is less than 5 minutes, it will not melt completely and undissolved residue and air bubbles will remain. If it is longer than 120 minutes, devitrification of the glass is likely to occur. The preferable melting time is about 10 to 60 minutes.
本発明において溶融時に発生する気泡を除去するために、真空装置により気泡を吸引しながら溶融することもできる。 In the present invention, in order to remove the bubbles generated at the time of melting, the bubbles can be sucked and melted by a vacuum device.
本発明の溶融温度は、従来のガラス製造方法である１０００℃以上の溶融法と比較すると十分低温であり、ガラス製造のエネルギーを抑制することができるため、環境負荷が小さく優れた製造方法である。 The melting temperature of the present invention is sufficiently low as compared with the melting method of 1000 ° C. or higher, which is a conventional glass manufacturing method, and the energy for glass manufacturing can be suppressed, so that the manufacturing method is excellent with a small environmental load. ..
上記方法で得られるスズ含有酸化物ガラス部材（Ｐ２Ｏ５−ＳｎＯ−Ｒ２Ｏ−ＭｘＯｙ系）は、透明性を持ち、溶融温度が５５０℃以下と低い。そのため、ＬＥＤの封止材料としても利用することが可能である。 Tin-containing oxide glass member obtained by the above methods (P 2 O 5 -SnO-R 2 O-M x O y type) has a transparency, it is less and less 550 ° C. melt temperature. Therefore, it can also be used as a sealing material for LEDs.
本発明の酸化物ガラスは、照明、光学部材、蛍光標識、ガラスコーティング、封止材、陶磁器、装飾用ガラス等にも使用可能である。 The oxide glass of the present invention can also be used for lighting, optical members, fluorescent labels, glass coatings, encapsulants, ceramics, decorative glass and the like.
本発明の酸化物ガラスは単独でも用いることができるが、他の材料を混合し、複合化した状態でも使用できる。 The oxide glass of the present invention can be used alone, but it can also be used in a composite state by mixing other materials.
本ガラスの透明性は例えば分光光度計（（株）日立製作所製 Ｕ−３５００）を用いて透過率を測定し、ＪＩＳ Ｒ３１０６の手法で可視光透過率を算出し、評価した。可視光透過率が７０％以上、好ましくは８０％以上が透明性ありとした。 The transparency of this glass was evaluated by measuring the transmission rate using, for example, a spectrophotometer (U-3500 manufactured by Hitachi, Ltd.), and calculating the visible light transmission rate by the method of JIS R3106. A visible light transmittance of 70% or more, preferably 80% or more was considered to be transparent.
本発明の酸化物ガラスの耐水性は、直径３０ｍｍ厚み５ｍｍに成形した試料ガラスを蒸留水に浸漬し、５０℃７２時間浸漬した後の単位面積当たりの重量減少値（ｇ／ｍｍ２）を測定し、評価した。耐水試験における重量減少値が１．０×１０−４ｇ/ｍｍ２以下、好ましくは１．０×１０−５ｇ/ｍｍ２以下が耐水性ありと判定した。 For the water resistance of the oxide glass of the present invention, the weight loss value (g / mm 2 ) per unit area after immersing the sample glass formed to a diameter of 30 mm and a thickness of 5 mm in distilled water and immersing it at 50 ° C. for 72 hours is measured. And evaluated. A weight reduction value of 1.0 × 10 -4 g / mm 2 or less, preferably 1.0 × 10 -5 g / mm 2 or less in the water resistance test was determined to be water resistant.
以下に本発明の実施例を示すことにより、本発明を詳細に説明するが、本発明はこれによって何ら限定されるものではない。 The present invention will be described in detail by showing examples of the present invention below, but the present invention is not limited thereto.
実施例１
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３５．０％、ＳｎＯ ５０．０％、Ｋ２Ｏ １５．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で１２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７１．０９％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は４．０１×１０−５ｇ／ｍｍ２であった。
Example 1
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 35.0%, SnO 50.0%, K 2 O 15.0% in mol% based on the oxide. , Potassium pyrophosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. While the precursor was placed in the above-mentioned beaker, it was heated and melted in the air at 550 ° C. for 120 minutes in a tabletop furnace, and the melt was poured into a stainless steel mold to obtain bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 71.09%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 4.01 × 10-5 g /. It was mm 2 .
実施例２
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ５０．０％、Ｌｉ２Ｏ ５．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７０．４５％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は５．２１×１０−５ｇ／ｍｍ２であった。
Example 2
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 45.0%, SnO 50.0%, Li 2 O 5.0% in mol% based on the oxide. , Lithium phosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 70.45%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 5.21 × 10-5 g /. It was mm 2 .
実施例３
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ４４．０％、Ｎａ２Ｏ ３．０％、Ｋ２Ｏ ８．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸ナトリウム、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８１．１９％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は４．８５×１０−５ｇ／ｍｍ２であった。
Example 3
85% so that the composition of the glass is P 2 O 5 45.0%, Sn O 44.0%, Na 2 O 3.0%, K 2 O 8.0% in terms of oxide-based mol%. Orthophosphoric acid, and tin oxide, sodium pyrophosphate, and potassium pyrophosphate were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 81.19%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 4.85 × 10-5 g /. It was mm 2 .
実施例４
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ５０．０％、ＳｎＯ ４４．０％、Ｋ２Ｏ ５．０％、Ｂ２Ｏ３ １．０％となるように、ピロリン酸、及び酸化第一錫、ピロリン酸カリウム、無水ホウ酸を秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４００℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７５．２３％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は７．０２×１０−５ｇ／ｍｍ２であった。
Example 4
Pyrrolinic so that the composition of the glass is P 2 O 5 50.0%, Sn O 44.0%, K 2 O 5.0%, B 2 O 3 1.0% in terms of oxide-based mol%. The acid, tin oxide, potassium pyrophosphate, and boric anhydride were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 400 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 75.23%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 7.02 × 10-5 g /. It was mm 2 .
実施例５
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４１．０％、ＳｎＯ ４４．０％、Ｌｉ２Ｏ ５．０％、Ｋ２Ｏ １０．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウム、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８４．２４％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は３．４０×１０−５ｇ／ｍｍ２であった。
Example 5
85% so that the composition of the glass is P 2 O 5 41.0%, Sn O 44.0%, Li 2 O 5.0%, K 2 O 10.0% in terms of oxide-based mol%. Orthophosphoric acid, and tin oxide, lithium phosphate, and potassium pyrophosphate were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 84.24%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 3.40 × 10-5 g /. It was mm 2 .
実施例６
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ３４．０％、Ｌｉ２Ｏ ５．０％、Ｋ２Ｏ １５．０％、ＳｉＯ２ １．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウム、ピロリン酸カリウム、ＴＥＯＳを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４００℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７６．０２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は４．４６×１０−５ｇ／ｍｍ２であった。
Example 6
The composition of the glass is P 2 O 5 45.0%, SnO 34.0%, Li 2 O 5.0%, K 2 O 15.0%, SiO 2 1.0% in mol% based on oxide. 85% orthophosphoric acid, tin oxide, lithium phosphate, potassium pyrophosphate, and TEOS were weighed so as to be. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 400 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 76.02%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 4.46 × 10-5 g /. It was mm 2 .
実施例７
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ５４．０％、Ｎａ２Ｏ ０．２％、ＢａＯ ０．８％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二ナトリウム、酸化バリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５００℃で１０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７５．８２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は５．６０×１０−５ｇ／ｍｍ２であった。
Example 7
The composition of the glass, in mole percent on the oxide basis, P 2 O 5 45.0%, SnO 54.0%, Na 2 O 0.2%, so that 0.8% BaO, 85% orthophosphoric acid , And stannous oxide, disodium hydrogen phosphate, and barium oxide were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 500 ° C. for 10 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 75.82%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 5.60 × 10-5 g /. It was mm 2 .
実施例８
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ５５．０％、ＳｎＯ ４４．０％、Ｌｉ２Ｏ ０．２％、Ａｌ２Ｏ３ ０．８％となるように、ピロリン酸、及び酸化第一錫、リン酸リチウム、水酸化アルミニウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中３５０℃で６０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８０．１２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は９．０１×１０−５ｇ／ｍｍ２であった。
Example 8
Pyrrolinate so that the composition of the glass is P 2 O 5 55.0%, Sn O 44.0%, Li 2 O 0.2%, Al 2 O 3 0.8% in terms of molar% based on oxides. The acid and stannous oxide, lithium phosphate and aluminum hydroxide were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. While the precursor was placed in the above-mentioned beaker, it was heated and melted in the air at 350 ° C. for 60 minutes in a tabletop furnace, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 80.12%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 9.01 × 10-5 g /. It was mm 2 .
実施例９
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ５９．０％、Ｎａ２Ｏ １．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二ナトリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７４．２６％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は８．５０×１０−６ｇ／ｍｍ２であった。
Example 9
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 40.0%, SnO 59.0%, Na 2 O 1.0% in mol% based on the oxide. , Disodium hydrogen phosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 74.26%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 8.50 × 10-6 g /. It was mm 2 .
実施例１０
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４１．０％、ＳｎＯ ５４．０％、Ｎａ２Ｏ ５．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二ナトリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７７．７３％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は６．５０×１０−５ｇ／ｍｍ２であった。
Example 10
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 41.0%, Sn O 54.0%, Na 2 O 5.0% in mol% based on the oxide. , Disodium hydrogen phosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 77.73%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 6.50 × 10-5 g /. It was mm 2 .
実施例１１
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３５．０％、ＳｎＯ ４５．０％、Ｋ２Ｏ １５．０％、ＺｎＯ ５．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二カリウム、酸化亜鉛を秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で６０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７２．５９％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は６．００×１０−５ｇ／ｍｍ２であった。
Example 11
The composition of the glass, in mole percent on the oxide basis, P 2 O 5 35.0%, SnO 45.0%, K 2 O 15.0%, so that 5.0% ZnO, 85% orthophosphoric acid , And stannous oxide, dipotassium hydrogen phosphate, and zinc oxide were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 550 ° C. for 60 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 72.59%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 6.00 × 10-5 g /. It was mm 2 .
実施例１２
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ５０．０％、Ｋ２Ｏ １０．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で１２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７８．８０％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は３．６０×１０−５ｇ／ｍｍ２であった。
Example 12
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 40.0%, Sn O 50.0%, K 2 O 10.0% in mol% based on the oxide. , Potassium pyrophosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 120 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 78.80%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 3.60 × 10-5 g /. It was mm 2 .
実施例１３
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ５０．０％、Ｋ２Ｏ ７．５％、Ｒｂ２Ｏ ２．５％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二カリウム、リン酸水素二ルビジウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８５．５６％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は３．００×１０−５ｇ／ｍｍ２であった。
Example 13
85% so that the composition of the glass is P 2 O 5 40.0%, Sn O 50.0%, K 2 O 7.5%, Rb 2 O 2.5% in terms of oxide-based mol%. Orthophosphoric acid, and stannous oxide, dipotassium hydrogen phosphate, and dirubidium hydrogen phosphate were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 85.56%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 3.00 × 10-5 g /. It was mm 2 .
実施例１４
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３８．０％、ＳｎＯ ４７．０％、Ｌｉ２Ｏ ５．０％、Ｋ２Ｏ １０．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウム、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で６０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８２．９２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は４．７０×１０−５ｇ／ｍｍ２であった。
Example 14
85% so that the composition of the glass is P 2 O 5 38.0%, Sn O 47.0%, Li 2 O 5.0%, K 2 O 10.0% in terms of oxide-based mol%. Orthophosphoric acid, and tin oxide, lithium phosphate, and potassium pyrophosphate were weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 60 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 82.92%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 4.70 × 10-5 g /. It was mm 2 .
実施例１５
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ５０．０％、Ｒｂ２Ｏ ５．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二ルビジウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４００℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８１．２３％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は８．５０×１０−５ｇ／ｍｍ２であった。
Example 15
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 45.0%, SnO 50.0%, Rb 2 O 5.0% in mol% based on the oxide. , Dirubidium hydrogen phosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 400 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 81.23%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 8.50 × 10-5 g /. It was mm 2 .
実施例１６
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３５．０％、ＳｎＯ ４４．０％、Ｋ２Ｏ ２０．０％、Ｙ２Ｏ３ ０．１％、Ｂ２Ｏ３ ０．９％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化イットリウム、無水ホウ酸を秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で６０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７２．６８％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は２．５０×１０−５ｇ／ｍｍ２であった。
Example 16
The composition of the glass is P 2 O 5 35.0%, SnO 44.0%, K 2 O 20.0%, Y 2 O 3 0.1%, B 2 O 30 in mol% based on oxide. 85% orthophosphoric acid and stannous oxide, potassium pyrophosphate, yttrium oxide, and boric anhydride were weighed to 9.9%. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 550 ° C. for 60 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 72.68%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 2.50 × 10-5 g /. It was mm 2 .
実施例１７
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ４８．０％、Ｌｉ２Ｏ ５．０％、ＣｅＯ２ ２．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウム、酸化セリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７５．６８％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は５．４３×１０−５ｇ／ｍｍ２であった。
Example 17
85% orthrin so that the composition of the glass is P 2 O 5 45.0%, SnO 48.0%, Li 2 O 5.0%, and CeO 2 2.0% in terms of oxide-based mol%. The acid and stannous oxide, lithium phosphate and cerium oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 75.68%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 5.43 × 10-5 g /. It was mm 2 .
実施例１８
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ４４．０％、Ｎａ２Ｏ １．０％、Ｋ２Ｏ ８．０％、Ｌａ２Ｏ３ ２．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸ナトリウム、ピロリン酸カリウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７９．５９％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は４．８９×１０−５ｇ／ｍｍ２であった。
Example 18
The composition of the glass is P 2 O 5 45.0%, SnO 44.0%, Na 2 O 1.0%, K 2 O 8.0%, La 2 O 3 2. 85% orthophosphoric acid, tin oxide, sodium pyrophosphate, potassium pyrophosphate, and lanthanum oxide were weighed so as to be 0%. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 79.59%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 4.89 × 10-5 g /. It was mm 2 .
実施例１９
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ４４．０％、Ｌｉ２Ｏ ５．０％、Ｋ２Ｏ １０．０％、ＣｅＯ２ ０．５％、Ｎｄ２Ｏ３ ０．５％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウム、ピロリン酸カリウム、酸化セリウム、酸化ネオジムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７１．３８％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は８．９２×１０−６ｇ／ｍｍ２であった。
Example 19
The composition of the glass is P 2 O 5 40.0%, SnO 44.0%, Li 2 O 5.0%, K 2 O 10.0%, CeO 2 0.5% in mol% based on oxide. , Nd 2 O 3 0.5%, 85% orthophosphoric acid, and stannous oxide, lithium phosphate, potassium pyrophosphate, cerium oxide, and neodymium oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 20 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 71.38%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 8.92 × 10-6 g /. It was mm 2 .
実施例２０
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ５５．０％、ＳｎＯ ３４．０％、Ｒｂ２Ｏ ６．０％、Ｌａ２Ｏ３ ５．０％となるように、ピロリン酸、及び酸化第一錫、リン酸水素二ルビジウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中３５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７１．０２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は８．５１×１０−５ｇ／ｍｍ２であった。
Example 20
Pyrrolinic so that the composition of the glass is P 2 O 5 55.0%, SnO 34.0%, Rb 2 O 6.0%, La 2 O 3 5.0% in terms of oxide-based mol%. The acid and stannous oxide, dirubidium hydrogen phosphate and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 350 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 71.02%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 8.51 × 10-5 g /. It was mm 2 .
実施例２１
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ４４．０％、Ｌｉ２Ｏ ９．０％、Ｌａ２Ｏ３ ２．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸リチウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５００℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８０．１４％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は７．９２×１０−５ｇ／ｍｍ２であった。
Example 21
85 so that the composition of the glass is P 2 O 5 45.0%, SnO 44.0%, Li 2 O 9.0%, La 2 O 3 2.0% in terms of oxide-based mol%. % Orthophosphoric acid, and tin oxide, lithium phosphate, and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 500 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 80.14%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 7.92 × 10-5 g /. It was mm 2 .
実施例２２
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ５９．０％、Ｎａ２Ｏ ０．２％、Ｙ２Ｏ３ ０．１％、ＢａＯ ０．７％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸ナトリウム、酸化イットリウム、酸化バリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８１．０６％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は５．１０×１０−６ｇ／ｍｍ２であった。
Example 22
The composition of the glass is P 2 O 5 40.0%, SnO 59.0%, Na 2 O 0.2%, Y 2 O 3 0.1%, BaO 0.7%, based on the oxide-based mol%. 85% orthophosphoric acid, and tin oxide, sodium pyrophosphate, yttrium oxide, and barium oxide were weighed so as to be. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 81.06%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 5.10 × 10-6 g /. It was mm 2 .
実施例２３
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３８．０％、ＳｎＯ ４６．９％、Ｋ２Ｏ １５．０％、Ｌａ２Ｏ３ ０．１％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８５．２２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は２．３０×１０−５ｇ／ｍｍ２であった。
Example 23
85 so that the composition of the glass is P 2 O 5 38.0%, Sn O 46.9%, K 2 O 15.0%, La 2 O 3 0.1% in terms of oxide-based mol%. % Orthophosphoric acid, and tin oxide, potassium pyrophosphate, and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 85.22%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 2.30 × 10-5 g /. It was mm 2 .
実施例２４
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．５％、ＳｎＯ ５４．０％、Ｎａ２Ｏ ５．０％、ＣｅＯ２ ０．５％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸ナトリウム、酸化セリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５００℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７６．７８％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は２．９０×１０−５ｇ／ｍｍ２であった。
Example 24
85% orthrin so that the composition of the glass is P 2 O 5 40.5%, SnO 54.0%, Na 2 O 5.0%, CeO 2 0.5% in mol% based on oxide. Acids and stannous oxide, sodium pyrophosphate and cerium oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 500 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 76.78%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 2.90 × 10-5 g /. It was mm 2 .
実施例２５
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３８．０％、ＳｎＯ ４６．０％、Ｋ２Ｏ １５．０％、ＣｅＯ２ ０．１％、Ｂ２Ｏ３ ０．９％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化セリウム、無水ホウ酸を秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８６．０３％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は４．６０×１０−５ｇ／ｍｍ２であった。
Example 25
The composition of the glass is P 2 O 5 38.0%, SnO 46.0%, K 2 O 15.0%, CeO 2 0.1%, B 2 O 3 0.9 in mol% based on oxide. 85% orthophosphoric acid, and stannous oxide, potassium pyrophosphate, cerium oxide, and boric anhydride were weighed so as to be%. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 86.03%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 4.60 × 10-5 g /. It was mm 2 .
実施例２６
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３５．０％、ＳｎＯ ４９．５％、Ｋ２Ｏ １５．０％、Ｌａ２Ｏ３ ０．５％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二カリウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で１２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７５．２３％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は５．３０×１０−５ｇ／ｍｍ２であった。
Example 26
85 so that the composition of the glass is P 2 O 5 35.0%, SnO 49.5%, K 2 O 15.0%, La 2 O 3 0.5% in terms of oxide-based mol%. % Orthophosphoric acid, tin oxide, dipotassium hydrogen phosphate, and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. While the precursor was placed in the above-mentioned beaker, it was heated and melted in the air at 550 ° C. for 120 minutes in a tabletop furnace, and the melt was poured into a stainless steel mold to obtain bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 75.23%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 5.30 × 10-5 g /. It was mm 2 .
実施例２７
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ４９．５％、Ｋ２Ｏ １０．０％、Ｌａ２Ｏ３ ０．５％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５００℃で１０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８３．７０％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値７．８０×１０−６ｇ／ｍｍ２であった。
Example 27
85 so that the composition of the glass is P 2 O 5 40.0%, SnO 49.5%, K 2 O 10.0%, La 2 O 3 0.5% in terms of oxide-based mol%. % Orthophosphoric acid, and tin oxide, potassium pyrophosphate, and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 500 ° C. for 10 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 83.70%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 7.80 × 10-6 g / mm. It was 2 .
実施例２８
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ４９．０％、Ｋ２Ｏ １０．０％、ＣｅＯ２ １．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化セリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８２．８８％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は１．６０×１０−６ｇ／ｍｍ２であった。
Example 28
85% orthophosphoric acid so that the composition of the glass is P 2 O 5 40.0%, SnO 49.0%, K 2 O 10.0%, and CeO 2 1.0% in terms of oxide-based mol%. The acid and stannous oxide, potassium pyrophosphate and cerium oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 82.88%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 1.60 × 10-6 g /. It was mm 2 .
実施例２９
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３９．５％、ＳｎＯ ５０．０％、Ｋ２Ｏ １０．０％、Ｎｄ２Ｏ３ ０．５％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化ネオジムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で６０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７８．０７％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は６．８７×１０−６ｇ／ｍｍ２であった。
Example 29
85 so that the composition of the glass is P 2 O 5 39.5%, Sn O 50.0%, K 2 O 10.0%, Nd 2 O 3 0.5% in mol% based on the oxide. % Orthophosphoric acid, and tin oxide, potassium pyrophosphate, and neodymium oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 60 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 78.07%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 6.87 × 10-6 g /. It was mm 2 .
実施例３０
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ５０．０％、Ｒｂ２Ｏ ５．０％、Ｌａ２Ｏ３ ５．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二ルビジウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で１２０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７２．３０％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は７．８９×１０−６ｇ／ｍｍ２であった。
Example 30
85 so that the composition of the glass is P 2 O 5 40.0%, SnO 50.0%, Rb 2 O 5.0%, La 2 O 3 5.0% in mol% based on the oxide. % Orthophosphoric acid, and tin oxide, dirubidium hydrogen phosphate, and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 120 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 72.30%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 7.89 × 10-6 g /. It was mm 2 .
比較例１
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ２５．０％、ＳｎＯ ７４．０％、Ｋ２Ｏ １．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で１２０分間加熱溶融したが、ガラス化せず、バルクガラスを得ることができなかった。
Comparative Example 1
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 25.0%, Sn O 74.0%, K 2 O 1.0% in mol% based on the oxide. , Potassium pyrophosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 550 ° C. for 120 minutes in the above-mentioned beaker while still in the beaker, but it was not vitrified and bulk glass could not be obtained.
比較例２
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ６５．０％、ＳｎＯ ３０．０％、Ｋ２Ｏ ５．０％となるように、８５％オルトリン酸、及び酸化第一錫、リン酸水素二カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中３５０℃で１０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、８０．１２％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は２．５０×１０−２ｇ／ｍｍ２であり、耐水性が劣る結果となった。
Comparative Example 2
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 65.0%, SnO 30.0%, K 2 O 5.0% in mol% based on the oxide. , Dipotassium hydrogen phosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 350 ° C. for 10 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 80.12%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 2.50 × 10 -2 g /. It was mm 2 , resulting in inferior water resistance.
比較例３
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４５．０％、ＳｎＯ ５５．０％となるように、８５％オルトリン酸、及び酸化第一錫を秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４００℃で１０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、７８．２３％であり、５０℃７２時間後の耐水性を測定したところ、重量減少値は６．８７×１０−４ｇ／ｍｍ２であり、耐水性が劣る結果となった。
Comparative Example 3
The composition of the glass, in mole percent on the oxide basis, P 2 O 5 45.0%, so that the SnO 55.0%, 85% orthophosphoric acid, and were weighed stannous oxide. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 400 ° C. for 10 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 78.23%, and when the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 6.87 × 10 -4 g /. It was mm 2 , resulting in inferior water resistance.
比較例４
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３５．０％、ＳｎＯ ６５．０％となるように、８５％オルトリン酸、及び酸化第一錫を秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４５０℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、１７．１３％となり、白濁ガラスであった。５０℃７２時間後の耐水性を測定したところ、重量減少値は５．８９×１０−４ｇ／ｍｍ２であり、耐水性が劣る結果となった。
Comparative Example 4
The composition of the glass, in mole percent on the oxide basis, P 2 O 5 35.0%, so that the SnO 65.0%, 85% orthophosphoric acid, and were weighed stannous oxide. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 450 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 17.13%, which was cloudy glass. When the water resistance after 72 hours at 50 ° C. was measured, the weight reduction value was 5.89 × 10 -4 g / mm 2 , resulting in inferior water resistance.
比較例５
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ３０．０％、ＳｎＯ ６０．０％、Ｋ２Ｏ １０．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で３０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で１２０分間加熱溶融したが、ガラス化せず、バルクガラスを得ることができなかった。
Comparative Example 5
85% orthophosphoric acid and stannous oxide so that the composition of the glass is P 2 O 5 30.0%, SnO 60.0%, K 2 O 10.0% in mol% based on the oxide. , Potassium pyrophosphate was weighed. Then, these weighed raw materials were mixed and stirred in a borosilicate beaker at 30 ° C. for 120 minutes to obtain a precursor. This precursor was heated and melted in the air at 550 ° C. for 120 minutes in the above-mentioned beaker while still in the beaker, but it was not vitrified and bulk glass could not be obtained.
比較例６
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ６３．０％、ＳｎＯ ３０．０％、Ｋ２Ｏ ５．０％、Ｌａ２Ｏ３ ２．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸カリウム、酸化ランタンを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中４００℃で３０分間加熱溶融し、融液をステンレス型に流し込むことで直径約３０ｍｍ、厚み５ｍｍのバルクガラスを得た。
このバルクガラスをＪＩＳ Ｒ３１０６に基づき可視光透過率を測定したところ、１５．８９％となり、白濁ガラスであった。５０℃７２時間後の耐水性を測定したところ、重量減少値は２．６８×１０−３ｇ／ｍｍ２であり、耐水性が劣る結果となった。
Comparative Example 6
85 so that the composition of the glass is P 2 O 5 63.0%, SnO 30.0%, K 2 O 5.0%, La 2 O 3 2.0% in terms of oxide-based mol%. % Orthophosphoric acid, and tin oxide, potassium pyrophosphate, and lanthanum oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 400 ° C. for 30 minutes in the above-mentioned beaker, and the melt was poured into a stainless steel mold to obtain a bulk glass having a diameter of about 30 mm and a thickness of 5 mm.
When the visible light transmittance of this bulk glass was measured based on JIS R3106, it was 15.89%, which was cloudy glass. When the water resistance after 72 hours at 50 ° C. was measured, the weight loss value was 2.68 × 10 -3 g / mm 2 , resulting in inferior water resistance.
比較例７
ガラスの組成が、酸化物基準のモル％で、Ｐ２Ｏ５ ４０．０％、ＳｎＯ ４５．０％、Ｎａ２Ｏ ５．０％、Ｙ２Ｏ３ １０．０％となるように、８５％オルトリン酸、及び酸化第一錫、ピロリン酸ナトリウム、酸化イットリウムを秤量した。次いで、これらの秤量した原料をホウ珪酸製ビーカー中で５０℃１２０分混合攪拌し、前駆体を得た。この前駆体を、前述のビーカーにいれたまま、卓上炉にて大気中５５０℃で６０分間加熱溶融したが、ガラス化せず、バルクガラスを得ることができなかった。
Comparative Example 7
85 so that the composition of the glass is P 2 O 5 40.0%, SnO 45.0%, Na 2 O 5.0%, Y 2 O 3 10.0% in mol% based on the oxide. % Orthophosphoric acid, and tin oxide, sodium pyrophosphate, and yttrium oxide were weighed. Then, these weighed raw materials were mixed and stirred at 50 ° C. for 120 minutes in a beaker made of borosilicate to obtain a precursor. This precursor was heated and melted in the air at 550 ° C. for 60 minutes in the above-mentioned beaker while still in the beaker, but it was not vitrified and bulk glass could not be obtained.
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